Acetylene carbonic-acid derivative.



CHARLES MOUREU, OF PARIS, FRANCE.

ACETYLENE CARBONlC-ACID DERIVATIVE.

Specification of Letters Patent.

Original application filed August 4,1902, Serial No. 118,392. Dividedand this application filed June 2'7, 1905. Serial No. 267.291.

I set forth in the followingPspecification.

technical purposes. patents I have made the following observa In myUnited States atent No. 749,800, dated January 19, 190451 have claimedthe acids issuing from N. heptin-l and N. octin- 1, and in my UnitedStates Patents Nos. 750,212 and 750,21 of same date, the .ethers derivedfrom t ese-acids as usefulfor Since taking out these tions, whichimprove or perfect my previous invention and which constitutes thesubject of my application, Serial No. 118,392, filed Au ust 4, 1902, ofwhich this application is a 'vision: I have found that instead ofstarting from the sodium derivatives of the N. heptin-L or N. octin-l ofthe original patent a similar technical effect can be obtained bytreating the sodium derivatives of the neighboring hydrocarbons withcarbon di oxid. In this way carboxylic acids of the acetylene familyare. obtained which are closely related :as isomers or homologues to theamyl and hexyl propiolic acid. The.

others of these new acids prepared by the well-known method ofetherification have a more or less pronounced odor resembling that ofthe ethers of the amyl and hexyl proiolic acids, which makes them usefulin peri lmery and similar industries.

The'*hydrocarbons used for the treatment with sodium are well-knownsubstances, the most of them prepared from the corresponding ketones.The action of the sodium takes place usually in the way described in myoriginal ap lication, Serial No. 68,944. In case of a s owaction of thesodium the sodium derivative can be obtained quicker by heating thehydrocarbon with the sodium to its boiling-point.

I will now proceed to give as an example the transforming of themethyl-5-hexanon-2 into the methyl hexin and into the acidmethyl-6-heptin-2-oic-1 or its ethers.

in the Bem'chte, Vol. 26, (1893,)

' In order that the compounds herein referred to may be expressed inclear, concise,

7 6 5 4 3 2 1 CH3-CHCH2CH,CEC.CO,H

is named methyl-fi-he tin-2-oic-1, [which Patented Feb. 5, 1907.

means that a hydrocar on of the acetylene series (heptin) is substitutedon its sixth carbon atom by methyl, has an acetylene 'group'on place 2,and a carbox lie or acid group on the first place. For revity the 'nameof the hydrocarbon is prefixed to the first designating terminationonly. This methyl hexanon has been pre ared by ketonic splitting ofethyl isobuty acetylacetat. It is mixed with pentachlorid of phosphorusand the chlorid is heated with caustic otash.

The crude hydrocar on well dried (for example, upon melted otash) isdissolved, if necessary, in a suitab e solvent, and there is added foreach molecule of the hydrocarbon an atom (or slightly more) sodium asfinely divided as possible. The reaction is allowed to take place byitself and is completed, if necessary, at a strong heat. times necessaryto heat at 120 150. Into the product thus obtained and which it isunnecessary to separate from the solvent a current of carbonic acidprevibusl-y dried is It is somecaused to pass for a sufficient time totransform the sodium derivative into the sodium salt of the new acidabove described. If care be taken to avoid loss of solvent byevaporation, the end of the reaction may be ascertained by the increaseof weight. The product of this reaction is allowed to drop 'ttle bylittle into water, so as to dissolve the sodium salt and, on the otherhand, to destroy any small amount of sodium which may have taken part inthe reaction. The

alkaline solution is then decanted oil and washed with a suitablesolvent (ether, for example.) It is then acidulated with a slight excessof strong acid (for example, sulfuric acid.) In this Way the new acid isset at liberty in the form of an oil, which floats upon the surface ofthe liquid. This product is extracted several tines with ether, (or other suitable solvent,) the ethereal liquors are united, washed with waterto remove any acidity of sulfuric acid, and the ethereal solution isdried as Well as possible by chlorid of calcium or any other analogousdrying agent. The ether is separated by distillation and the residuepurified by fractional distillation in vacuo.

The ethers of this acid can be prepared directly by the knownetherification processior example, by simply heating the alcohol withthe acid or through the inter mediation of an etherifying agent, such assulfuric acid. In this way I have prepared, by starting, from. heInethVl-5heXin-1, the acid methyl-6- from the rnethyl-6-heptin-1, theacid methyl- 7-octin-2-oic-1 These acids and their ethers are, with oneexception, O1l V, colorless, or yellowish liquids, i

almost insoluble in water, soluble in alcohol,

ether, benzol, and gasolene.

Boiling Specific point. Pressure gravity Methyl-G-heptln-Z-oic-l 142-417-19 mm. 0 905 (18 C Its methylic other 98100 -18 mm. 0. 942 (0) Itscthyllc other. 110-112 mm. 0.929 (0) Methyl-$00131n-2-0ic-1 100-17236-38 mm. 0.960 (0) Its nuthyllc other. 12.127 29-31 mm. 0.933 (0) Itsetliyllc other. v 155-137" 28-30 mm. 0.922 (0) Dekin2oic1 i 104-10818-20 mm. 0. 941 (17) Its methylie other. 133-135" 10-21 mm. 0 926 (0)Its othylic other. 143-140 10-21 mm. 0.917 (0) Dodelrin-2-oic-1Moltingpoint....'. i i

Its methyl ether. 108-172 29-30 mm. 0.916 (0) Its ethyl ether 105-109"19-21 mm. 0.908 (0) What I claim is- 1. As new bodies theabove-described ethers of isoamyl propiolic acid, methyl-6-heptin-2-oic-1, said .ethers being oily, practically colorless,transparent li ui s of a more or less pronounced agreea le'arom-a,lighter than water, almost insoluble in same, easily soluble in alcohol,ether, benzol and gasolene, their boiling-points being 110 centigradeunder fifteen millimeters pressure. j

2. As a new body the above-described methylic ether of isoamyl propiolicacid, methyl-6-heptin-2-oic-1, said ether being an oily, practicallycolorless, transparent liquid of an agreeablearoma, boiling at 98-100Centigrade under 16-18 niillineters pressure, having a specific gravity0.942 (0,) the $211116 being almost insoluble in water, easily Tolublein alcohol, ether, benzol and gasocne.

In testimony whereof I have signed this specification in the presence oftwo subscribing witnesses.

CHARLES MOUREU.

Witnesses:

J ULES ARMENGAUD, Jeune, IIANSON O. Come.

